TW201638260A - Resin film-forming sheet, resin film-forming composite sheet, and silicon wafer regeneration method - Google Patents

Abstract

Provided is a resin film-forming sheet to be applied on a silicon wafer for forming a resin film on said silicon wafer, wherein the following conditions (I)-(III) are satisfied and the sheet has excellent re-workability and edge adhesiveness. Condition (I): The surface roughness (Ra) of the surface ([alpha]) of the resin film-forming sheet on the side that is applied on the silicon wafer is 50 nm or less. Condition (II): The adhesive force ([alpha]1) of the surface ([alpha]) of the resin film-forming sheet with respect to the silicon wafer is 1.0-7.0 N/25 mm. Condition (III): The adhesive force ([beta]1) of the surface ([beta]) of the resin film-forming sheet, on the side opposite to the side that is applied on the silicon wafer, with respect to the adhesive layer of an adhesive sheet having an adhesive layer of 10-50 [mu]m thickness formed from a specified adhesive is at least 4.0 N/25 mm.

Description

Resin film forming sheet, resin film forming composite sheet, and wafer wafer reproducing method

The present invention relates to a sheet for forming a resin film, and a composite sheet for forming a resin film for forming the sheet for forming a resin film, and a method for regenerating a tantalum wafer.

In recent years, the manufacture of semiconductor devices using a so-called flip-chip packaging method has been carried out. In the flip-chip method, a semiconductor wafer having an electrode such as a bump mounted on a circuit surface of a substrate (hereinafter also referred to simply as "wafer") is bonded to the substrate. Therefore, the surface on the opposite side to the side where the wafer is bonded to the substrate (hereinafter also referred to as "the back surface of the wafer") is exposed.

A resin film made of an organic material is formed on the back surface of the exposed wafer, and the wafer as the resin film is packaged in a semiconductor device. The resin film can perform the functions of preventing the cracking step or the cracking after the packaging as a protective film, or the subsequent use of the wafer obtained on the substrate portion or another semiconductor wafer or the like. Then the function of the film.

Generally, the wafer with the resin film is applied onto the back surface of the wafer by a spin coating method or the like to form a coating film, and then the coating film is dried and cured to form a resin film, and the cutting film is formed. It is manufactured by obtaining a wafer with a resin film.

In addition, the curable resin film-forming sheet may be attached to the back surface of the wafer, and the resin film-forming sheet may be cured by irradiation or heating of the energy line before and after the dicing of the wafer to obtain a resin film. A wafer with a resin film or a wafer with a resin film is produced.

As a resin film material which also functions as a protective film or a film on the back surface of the wafer or the back surface of the wafer, various sheets for forming a resin film have been proposed.

For example, Patent Document 1 discloses that an energy ray-curable protective film forming layer containing a polymer component composed of an acrylic copolymer, an energy ray-curable component, a dye or a pigment, an inorganic filler, and a photopolymerization initiator has A wafer protective film composed of two release sheets sandwiched therebetween.

According to Patent Document 1, the wafer protective film is formed by a radiation line, and can form a protective film having excellent laser mark visibility, hardness, and adhesion to a wafer, and is compatible with conventional wafer protection. The comparison of the films simplifies the steps.

Further, Patent Document 2 discloses a dicing tape having a substrate and an adhesive layer, and a dicing tape integrated with a dicing tape of a dicing tape and having a specific elastic modulus. Round back protective film.

According to Patent Document 2, the wafer back surface protective film is semiconductive In the cutting step of the bulk wafer, the holding force with the semiconductor wafer is good.

[Previous Technical Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2009-138026

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2010-199543

In the step of attaching the protective film described in Patent Documents 1 and 2 to the wafer, when the position of the protective film attached to the wafer is displaced, a state in which foreign matter adheres to the wafer is caused, for example, The protective film is attached to the wafer in a state in which foreign matter is also contained. In such cases, it is difficult to reprocess (re-peel) the wafer from the protective film once attached to the wafer.

In particular, the protective film disclosed in Patent Documents 1 and 2 is intended to improve the adhesion to the wafer at the time of attachment or the adhesion between the wafer and the wafer, and is attached to the wafer once attached to the wafer. The density of the circle is high, so it is very difficult to reprocess.

That is, when the protective film adhered to the wafer is forcibly peeled off, the wafer may be damaged, or a part of the protective film may remain on the wafer even if the wafer peeling protective film is not damaged.

In the protective films described in Patent Documents 1 and 2, there is a review of the adhesion from the wafer at the time of attachment or the adhesion of the wafer after attachment, but no relevant Once attached to the wafer Review of the reworkability of protective films.

In addition, it is necessary to pay attention to the necessity of reattaching the protective film immediately after attaching the protective film and the wafer, and the state in which the laminated body of the protective film is attached to the wafer after being left for 24 hours or so is also noticed. many.

After the protective film is attached to the wafer, the adhesion of the wafer to the protective film is improved as time passes, so it is generally difficult to reprocess the protective film.

In addition, it is also possible to consider the reworkability after attaching to the silicon wafer, and to use a rough-designed protective film on the surface of the wafer attachment side, so that the end of the film is attached to the wafer and the end is easy. Floating or peeling occurs, which causes a problem that the end adhesion is deteriorated.

The present invention has been made in view of the above-mentioned problems, and it is an object of the present invention to provide a sheet for forming a resin film which is excellent in reworkability and end-sealing properties, and a sheet for forming a resin film on the support sheet. Composite sheets, and methods for regenerating tantalum wafers.

The present inventors have found that a sheet for forming a resin film having an adhesive property which is adhered to the surface roughness of the surface on the side to which the wafer is attached and the adhesion of the wafer, and to the surface layer The adhesion of the adhesive layer of the other surface of the other surface of the adhesive sheet can solve the above problems and complete the present invention.

That is, the present invention provides the following [1] to [10].

[1] A sheet for forming a resin film for attaching to a tantalum wafer and forming a sheet of a resin film on the tantalum wafer, and satisfying the following requirements (I) to (III), and (I) The surface roughness (Ra) of the surface (α) of the resin film-forming sheet and the side of the ruthenium wafer attached is 50 nm or less, and the surface (α) of the surface of the resin film-forming sheet (α) The adhesion of the wafer (α 1) is 1.0 to 7.0 N/25 mm, and the surface ( β ) of the surface of the resin film-forming sheet is opposite to the side of the wafer-attached side. The adhesive layer of the formed adhesive sheet having the adhesive layer has an adhesive force ( β 1) of 4.0 N/25 mm or more, and the adhesive contains a structural unit derived from butyl acrylate and acrylic acid, and the mass average molecular weight is 100 parts by mass of the acrylic resin of 600,000 to 1,000,000, and 0.01 to 10 parts by mass of the crosslinking agent, and the adhesive sheet has an adhesive layer having a thickness of 10 to 50 μm.

[2] The sheet for forming a resin film according to [1], wherein the storage elastic modulus at 23 ° C is 0.10 to 20 GPa.

[3] The sheet for forming a resin film according to [1] or [2], wherein the surface ( β ) of the sheet for forming a resin film has a contact angle with respect to water of 70 to 110°.

[4] The sheet for forming a resin film according to any one of [1] to [3], which comprises a polymer component (A) and a curable component (B).

[5] The sheet for forming a resin film according to [4], wherein the polymer component (A) contains an acrylic polymer (A1).

[6] The sheet for forming a resin film according to [5], wherein the acrylic polymer (A1) has a structural unit derived from an alkyl (meth) acrylate (a1) and a structural unit derived from a nitrile monomer. (a2) an acrylic copolymer.

[7] The sheet for forming a resin film according to any one of [1] to [6], which is used for forming a protective film on a germanium wafer.

[8] A composite sheet for forming a resin film, which comprises a sheet for forming a resin film according to any one of [1] to [7].

[9] The composite sheet for forming a resin film according to [8], wherein the sheet for forming a resin film has a configuration in which two sheets of support sheets are sandwiched.

[10] A method for regenerating a tantalum wafer, which is a laminate of a surface (α) of a sheet for forming a resin film according to any one of [1] to [7], which is directly attached to a wafer. The resin film forming sheet is used to reproduce a tantalum wafer, and has the following steps (1) to (2), and the step (1): the surface ( β ) of the resin film forming sheet of the laminate And the step of attaching the adhesive layer having the adhesive sheet of the substrate and the adhesive layer, and the step (2): attaching to the surface ( β ) of the sheet for forming a resin film in the stretching step (1) The adhesive sheet is used to reprocess the resin film forming sheet attached to the tantalum wafer.

The sheet for forming a resin film of the present invention is reworkability and end Excellent adhesion.

Therefore, when the resin film-forming sheet of the present invention is attached to the tantalum wafer, the necessity of reattachment is not caused, the wafer is not damaged, and the adhesion remaining on the tantalum wafer can be suppressed. There is a portion of the sheet for forming a resin film, and the sheet for forming a resin film can be further processed from the tantalum wafer. As a result, the tantalum wafer after reworking the sheet for forming a resin film can be reused.

In the present specification, the "reworked resin film forming sheet" means a sheet for forming a resin film which is adhered to the tantalum wafer.

In addition, the "reworkability of the sheet for forming a resin film" means that after the wafer is attached to the wafer, the wafer is not damaged during the reworking, and a portion of the sheet for forming a resin film remains on the wafer. The nature of the stripping.

1a, 1b, 1c, 1d‧‧‧ composite film for resin film formation

10‧‧‧Sheet film for resin film formation

11, 11' ‧ ‧ support sheet

12‧‧‧ Fixture layer

Fig. 1 is a cross-sectional view showing a composite sheet for forming a resin film according to an aspect of the present invention.

In the description of the present specification, the values of the mass average molecular weight (Mw) and the number average molecular weight (Mn) of each component are values in terms of standard polystyrene measured by a gel permeation chromatography (GPC) method, specifically based on The values measured in the methods of the examples are described.

In addition, in the present specification, for example, "(meth) acrylate" means a term used to mean both "acrylate" and "methacrylate". Use, the same is true for other similar terms.

In the present specification, "energy ray" means, for example, ultraviolet rays or electron beam lines, and ultraviolet rays are preferred.

[Resin film forming sheet]

The sheet for forming a resin film of the present invention is used for attaching to a tantalum wafer, and forming a sheet of a resin film on the tantalum wafer, and satisfying the following requirements (I) to (III), and the element (I): The surface roughness (Ra) of the surface (α) of the sheet for forming a resin film and the side of the ruthenium wafer attached is 50 nm or less (hereinafter also referred to as "surface roughness (Ra) of surface (α)"), (II): The adhesion (α 1) of the surface (α) of the sheet for forming a resin film to the wafer is 1.0 to 7.0 N/25 mm (hereinafter also referred to simply as the adhesion of the surface (α) (α) 1)"), the element (III): the surface of the resin film-forming sheet ( β ) and the adhesive sheet having an adhesive layer formed of an adhesive on the side opposite to the side of the enamel wafer attached side The adhesion of the layer ( β 1) (hereinafter also referred to as "the adhesion of the surface ( β ) ( β 1)") is 4.0 N/25 mm or more, and the above adhesive contains a source derived from butyl acrylate and acrylic acid. The structural unit is 100 parts by mass of an acrylic resin having a mass average molecular weight of 600,000 to 1,000,000, and 0.01 to 10 parts by mass of a crosslinking agent, and the adhesive sheet has an adhesive layer having a thickness of 10 to 50 μm. .

The surface (α) of the sheet for forming a resin film of the present invention is bonded to the side of the ruthenium wafer, and the surface ( β ) is attached to the ruthenium wafer to form the sheet for forming a resin film from the ruthenium wafer. Reattached to the attachment surface attached to the adhesive layer of the adhesive sheet.

Further, the form of the sheet for forming a resin film of the present invention is not particularly limited, and may be, for example, a long tape-like label or a leaf label.

Further, the sheet for forming a resin film according to an aspect of the present invention may be a single layer sheet formed by forming one layer of one type of composition, or may be composed of two or more layers formed of two or more types of compositions. Multi-layered sheet.

Further, when the sheet for forming a resin film according to an aspect of the present invention is a multi-layered sheet composed of two or more layers, the composition (α') and the surface ( β ) of the material forming the layer on the surface (α) side. It is preferable that the composition ( β ') of the material forming the layer on the side is adapted to the type (I) to (III) of the above-mentioned requirements, and the type or blending amount of the component to be contained is preferably adjusted. Therefore, it is preferred that the composition (α') and the composition ( β ') are different from each other.

<Requirement (I)>

By the above-mentioned requirement (I), the resin film-forming sheet of the present invention can be prevented from being lifted or peeled off at the end portion of the wafer after being attached to the wafer, and the end portion is excellent in adhesion.

In other words, when the surface roughness (Ra) of the surface (α) exceeds 50 nm, when the obtained resin film-forming sheet is attached to the tantalum wafer, the adhesion to the tantalum wafer is insufficient, which is particularly The end of the wafer is easy to produce Float or peel off, and deteriorate the end adhesion. When the adhesion is lowered, in particular, when the end sealability is lowered, the washing water used for cutting enters the interface between the resin film forming sheet and the tantalum wafer, thereby causing contamination of the wafer. The surface is either the cause of the chipping during cutting.

From the above viewpoint, the surface roughness (Ra) of the surface (α) of the sheet for forming a resin film which is one aspect of the present invention is preferably 40 nm or less, preferably 35 nm or less, more preferably 30 nm or less, and most preferably It is 25 nm or less.

In addition, the surface roughness (Ra) of the surface (α) is preferably 5 nm or more, preferably 10 nm or more, and more preferably 15 nm or more from the viewpoint of setting the sheet for forming a resin film to improve the reworkability. .

Further, the surface roughness (Ra) of the surface (α) in the present specification is a value measured in accordance with JIS B0601:2001, and more specifically means a value measured by the method described in the examples.

In addition, the surface roughness (Ra) of the surface (α) can be adjusted by appropriately setting the type, average particle diameter, and content of the fine particle component such as an inorganic filler or a coloring agent contained in the sheet for forming a resin film. . In addition, the method of attaching the uneven surface of the peeling film having the rough uneven surface of the surface to the surface (α) of the sheet for forming a resin film and transferring the uneven shape can be adjusted.

<Requirement (II)>

The sheet for forming a resin film of the present invention can maintain good adhesion to the ruthenium wafer while satisfying the requirement (II), particularly the end portion. Adhesiveness can be processed even after 24 hours or so.

For example, as disclosed in Patent Documents 1 and 2, the conventional resin film-forming sheet is often used for the purpose of improving the adhesion and retention of the tantalum wafer, and is used to enhance the specificity of the element (II). The material design of the value of the adhesion of the surface (α).

However, when the adhesion (α 1) of the surface (α) exceeds 7.0 N/25 mm, the reworking of the obtained resin film-forming sheet after sticking to the tantalum wafer tends to be difficult. In particular, since the adhesion between the silicon wafer and the resin film forming sheet is increased as the time elapses after the bonding to the wafer, the resin film forming sheet is forcibly reprocessed from the silicon wafer. The force of reprocessing can damage the wafer.

On the other hand, when the adhesion (α 1) of the surface (α) is less than 1.0 N/25 mm, the adhesion to the tantalum wafer is insufficient, and in particular, the obtained sheet for forming a resin film is attached to the twin crystal. In the case of a circle, the end portion of the wafer is likely to float or peel off, and the end portion is deteriorated.

Then, in the sheet for forming a resin film of the present invention, the adhesion force (α 1) of the surface (α) is adjusted to a range specified by the element (II).

The adhesion (α 1) of the surface (α) of the sheet for forming a resin film according to an aspect of the present invention is such that the adhesion to the wafer is improved, in particular, the adhesion of the wafer to the wafer is carried out. From the viewpoint of setting the sheet for forming a resin film for adhesion, it is preferably 1.3 N/25 mm or more, preferably 1.5 N/25 mm or more, more preferably 1.8 N/25 mm or more, and most preferably 2.0 N/25 mm or more. From the viewpoint of setting the sheet for forming a resin film for improving reworkability, it is preferably 6.8 N/25 mm or less, preferably 6.5N/25mm or less, more preferably 6.0N/25mm or less, and most preferably 5.5N/25mm or less.

Further, the adhesion (α 1) of the surface (α) in the present specification means the value measured by the method described in the examples.

In addition, the adhesive force (α 1) of the surface (α) is a polymer component, a curable component, and an inorganic filler which are contained in the composition of the material for forming the layer on the surface (α) side of the sheet for forming a resin film. The type or content of the additive and the like can be adjusted as shown in the above range. Specifically, it can be easily adjusted by considering the items of the respective components contained in the sheet for forming a resin film.

<Requirement (III)>

The sheet for forming a resin film of the present invention is a reworkable person even if it has been satisfied for about 24 hours by satisfying the requirement (III).

When the sheet for forming a resin film of the present invention is attached to a tantalum wafer, and the sheet for forming a resin film needs to be peeled off again, the surface of the sheet for forming a resin film ( β ) is attached to the adhesive sheet of the general-purpose adhesive sheet. The agent layer can rework the resin film forming sheet from the tantalum wafer by stretching the adhesive sheet.

In this case, when the adhesion ( β 1) of the surface ( β ) is less than 4.0 N/25 mm, the adhesive layer of the adhesive sheet is attached to the surface ( β ), and the resin film is peeled off together with the adhesive sheet. In the sheet, a part of the resin film forming sheet tends to remain on the tantalum wafer, and the processed wafer cannot be reused.

From the above viewpoints, the adhesion ( β 1) of the surface ( β ) of the sheet for forming a resin film of one aspect of the present invention is preferably 4.5 N/25 mm or more, preferably 5.0 N/25 mm or more.

Further, the upper limit of the adhesion force of the surface ( β ) is not particularly limited, but the adhesion force ( β 1) of the surface ( β ) is usually 20 N/25 mm or less.

The adhesion ( β 1) of the surface ( β ) of the sheet for forming a resin film specified by the element (III) is an adhesion of an adhesive sheet having an adhesive layer formed of an adhesive to the adhesive layer, and an adhesive system. The present invention comprises a structural unit derived from butyl acrylate and acrylic acid, 100 parts by mass of an acrylate resin having a mass average molecular weight of 600,000 to 1,000,000, and 0.01 to 10 parts by mass of a crosslinking agent, and an adhesive sheet having a thickness of 10 to 50 μm. Adhesive layer.

The adhesive composition is a commercially available general acrylate adhesive, and the component (III) is the adhesion of a specific surface ( β ) to an adhesive layer formed of a general acrylate adhesive.

Further, the adhesive which satisfies the requirement (III) is a very general acrylate-based adhesive which is widely distributed on the market.

Therefore, when the resin film-forming sheet of the present invention is reprocessed from a tantalum wafer, the adhesive sheet used is very selective, and an adhesive layer having a general adhesive layer composed of an acrylate-based adhesive can be used. Reprocessing.

Further, more specifically, the adhesion of the surface ( β ) ( β 1 ) means a value measured by the method described in the examples.

Further, the adhesion surface (beta]) of (β 1) is suitably selected based resin film-forming polymer component with a surface of the sheet to form a layer of the composition (beta]) side of the material contained, the curable component, an inorganic filler, and The type or content of the additive may be adjusted to the above range. Specifically, it can be easily adjusted by considering the items of the respective components contained in the sheet for forming a resin film.

One aspect of the present invention is formed of a resin film sheet, so that the resin film is then further processed to enhance the viewpoint of forming the sheet, the adhesion surface (beta]) of (β 1) than the surface-based ([alpha]) of The adhesion of the adhesive force (α 1) is higher.

From the above point of view, the difference between the adhesion force ( β 1) and the adhesion force (α 1) [( β 1) - (α 1)] is preferably 0 to 8.0 N/25 mm, preferably 0.1 to 7.0 N. /25mm, more preferably 0.5~6.0N/25mm, and most preferably 1.5~5.5N/25mm.

The storage elastic modulus at 23 ° C of the sheet for forming a resin film of one aspect of the present invention is preferably from 0.10 to 20 GPa, preferably from 0.15 to 15 GPa, more preferably from 0.20 to 10 GPa, most preferably from 0.30 to 5.0 GPa.

When the storage elastic modulus is 0.10 GPa or more, the resin film-forming sheet is attached to the ruthenium wafer, and when it is peeled again, the deformation of the resin film-forming sheet is suppressed, and a part of the wafer is not left. The sheet for forming a resin film can be peeled off from the sheet for forming a resin film.

On the other hand, if the storage elastic modulus is 20 GPa or less, the adhesion to the silicon wafer can be favorably set.

Further, the storage elastic modulus of the sheet for forming a resin film in the present specification means a value measured by the method described in the examples.

The contact angle of the surface ( β ) of the sheet for forming a resin film according to one aspect of the present invention is preferably 70 to 110° from the viewpoint of a sheet for forming a resin film which improves reworkability. Preferably, it is 75 to 100 degrees, more preferably 80 to 95 degrees, and most preferably 83 to 93 degrees.

Further, the contact angle with respect to water on the surface ( β ) of the sheet for forming a resin film in the present specification means a value measured by the method described in the examples.

<Composition component of sheet for forming a resin film>

The sheet for forming a resin film according to an aspect of the present invention is not particularly limited as long as it has the surface (α) and the surface ( β ) of the requirements (I) to (III), but contains the polymer component (A) and The curable component (B) is preferred.

Further, the sheet for forming a resin film according to an aspect of the present invention does not impair the effects of the present invention from the viewpoint of satisfying the formation of the surface (α) and the surface ( β ) of the components (I) to (III). The above components (A) and (B) may be contained in the range, and may also contain an inorganic filler (C), a colorant (D), a coupling agent (E), a leveling agent (F), and a general-purpose additive ( One or more of G).

Hereinafter, the above components (A) to (G) which are constituent components of the sheet for forming a resin film which is one aspect of the present invention will be described.

[Polymer component (A)]

In the present specification, the "polymer component" means a compound having a mass average molecular weight (Mw) of 20,000 or more and having at least one repeating unit.

The sheet for forming a resin film used in one aspect of the present invention is provided with a polymer component (A), imparts warpage and film-forming properties, and has a good sheet-like shape retention property. As a result, the storage elastic modulus at 23 ° C of the sheet for forming a resin film can be adjusted to the above range.

The mass average molecular weight (Mw) of the polymer component (A) is preferably 20,000 or more from the viewpoint of adjusting the storage elastic modulus at 23 ° C of the obtained sheet for forming a resin film to the above range. The best is 20,000 to 3 million, more preferably 50,000 to 2 million, and the best is 100,000 to 1.5 million.

The content of the polymer component (A) in the sheet for forming a resin film of the aspect of the invention is preferably from 5 to 50% by mass, preferably from 5 to 50% by mass, based on the total amount of the sheet for forming a resin film (100% by mass). 8 to 40% by mass, more preferably 10 to 35% by mass, most preferably 15 to 30% by mass.

In the present specification, the "content of the component (A) relative to the total amount of the sheet for forming a resin film" is the component of the total amount of the active ingredient in the composition of the material for forming the sheet for forming a resin film ( The content of A) is synonymous and the content of the other ingredients described below is also synonymous.

In other words, the phrase "the total amount (100% by mass) of the sheet for forming a resin film" of the content of each of the specific components may be replaced by the composition of the material for forming the sheet for forming a resin film. Active ingredient The statement of the total amount (100% by mass) is synonymous with the specific content.

In addition, the above-mentioned "active ingredient" means a component which removes a substance which does not affect the physical properties of the film which is directly or indirectly reacted or formed by a solvent in the composition, and specifically means a solvent such as water or an organic solvent. Other ingredients.

The polymer component (A) preferably contains an acrylic polymer (A1), and may contain a polyester other than the acrylic polymer (A1), a phenoxy resin, a polycarbonate, a polyether, a polyurethane, and a polyfluorene. Non-acrylic polymer (A2) such as oxyalkylene or rubber-based polymer.

These polymer components can be used individually or in combination of 2 or more types.

The total amount (100% by mass) of the polymer component (A) contained in the sheet for forming a resin film according to an aspect of the present invention is preferably 50 to 100% by mass based on the content of the acrylic polymer (A1). It is preferably 60 to 100% by mass, more preferably 70 to 100% by mass, most preferably 80 to 100% by mass.

(acrylic polymer (A1))

The mass average molecular weight (Mw) of the acrylic polymer (A1) is adjusted from the storage elastic modulus of 23 ° C of the sheet for forming a resin film to the above range by imparting warpage and film forming properties to the sheet for forming a resin film. From the point of view, the best is 20,000 to 3 million, preferably 100,000 to 1.5 million, more preferably 150,000 to 1.2 million, and the best is 250,000 to 1 million.

The acrylic polymer (A1) has a structural unit derived from an alkyl (meth) acrylate from the viewpoint of adjusting the adhesion (α 1) and ( β 1) of the sheet for forming a resin film to the above range. The acrylic polymer (a1) is preferably a structural unit (a1) and a monomer derived from a nitrile monomer, from the viewpoint of adjusting the adhesion (α 1) of the sheet for forming a resin film to the above range. The acrylic copolymer of the structural unit (a2) is more preferable.

Further, the acrylic polymer (A1) used in one aspect of the present invention may further have an alkyl (meth) acrylate and not a nitrile monomer in addition to the structural units (a1) and (a2). It is derived from the structural unit (a3) of other monomers.

Further, the acrylic polymer (A1) may be used singly or in combination of two or more.

Further, in the case of the acrylic polymer (A1)-based copolymer, the form of the copolymer may be any of a block copolymer, a random copolymer, an alternating copolymer, and a graft copolymer.

(Structural unit (a1))

The number of carbon atoms of the alkyl group (meth) acrylate constituting the structural unit (a1) is preferably from 1 to 18, from the viewpoint of imparting warpage and film forming properties to the sheet for forming a resin film. Good for 1~12, better for 1~8.

Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and pentyl. (Meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-fluorenyl (methyl) propyl Alkenoate, isodecyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, and the like.

Further, these alkyl (meth) acrylates may be used singly or in combination of two or more.

Among these, an alkyl (meth) acrylate having an alkyl group having 1 to 3 carbon atoms is preferred, and a methyl (meth) acrylate is more preferred.

The content of the structural unit (a1-1) derived from the alkylalkyl (meth) acrylate having a carbon number of 1 to 3 in the acrylic polymer (A1) is relative to the entire acrylic polymer (A1). The structural unit (100% by mass) is preferably from 5 to 99% by mass, preferably from 10 to 98% by mass, more preferably from 20 to 97% by mass, most preferably from 25 to 97% by mass.

The content of the structural unit (a1) in the acrylic polymer (A1) is preferably 50% by mass or more, preferably 50 to 99% by mass based on the total structural unit (100% by mass) of the acrylic polymer (A1). %, more preferably 55 to 98% by mass, most preferably 60 to 97% by mass.

(Structural unit (a2))

Examples of the nitrile monomer constituting the structural unit (a2) include (meth)acrylonitrile, α-chloro(meth)acrylonitrile, α-ethoxy(methyl)acrylonitrile, and fumaronitrile.

Further, these nitrile-based single systems may be used alone or in combination of two or more.

The medium (meth)acrylonitrile is preferred.

The acrylic polymer (A1) is derived from a nitrile monomer The content of the structural unit (a2) is preferably from 1 to 50% by mass, preferably from 5 to 45% by mass, more preferably from 10 to 42%, based on the total structural unit (100% by mass) of the acrylic polymer (A1). The mass% is more preferably 15 to 40% by mass, and most preferably 20 to 35% by mass.

When the content of the structural unit (a2) is 1% by mass or more, the adhesion (α 1) of the surface (α) of the obtained sheet for forming a resin film is easily adjusted to the above range. On the other hand, when the content of the structural unit (a2) is 50% by mass or less, the adhesion ( β 1) of the surface ( β ) of the sheet for forming a resin film is easily adjusted to the above range.

(Structural unit (a3))

In the range in which the acrylic polymer (A1) does not impair the effects of the present invention, in addition to the above structural units (a1) and (a2), the alkyl (meth) acrylate and the nitrile monomer may also be derived. It is not equivalent to the structural unit of other monomers (a3).

Examples of the other monomer constituting the structural unit (a3) include a functional group-containing monomer having a functional group such as a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and an epoxy group-containing monomer; vinyl acetate and vinyl propionate; Vinyl ester monomer; olefin monomer such as ethylene, propylene, isobutylene; aromatic vinyl monomer such as styrene, methyl styrene or vinyl toluene: diene monomer such as butadiene or isoprene Body and so on.

From the viewpoint of adjusting the adhesion forces (α 1) and ( β 1) of the sheet for forming a resin film to the above range, the acrylic polymer (A1) used in one aspect of the present invention contains a single derived from a hydroxyl group. The structural unit (a3-1) of the body is preferred.

Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxybutyrate. Hydroxyalkyl (meth) acrylates such as (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; vinyl alcohol, allyl alcohol, etc. Unsaturated alcohols, etc.

These 2-hydroxyethyl (meth) acrylates are preferred.

The content of the structural unit (a3-1) derived from the hydroxyl group-containing monomer in the acrylic polymer (A1) is adjusted from the adhesion (α 1) and ( β 1) of the sheet for forming a resin film to the above range. The total structural unit (100% by mass) of the acrylic polymer (A1) is preferably from 0.5 to 30% by mass, preferably from 1 to 25% by mass, more preferably from 2 to 20% by mass, most preferably. It is 3 to 15% by mass, and particularly preferably 3.5 to 12% by mass.

In addition, when the content of the structural unit derived from the epoxy group-containing monomer in the acrylic polymer (A1) is increased, the adhesion between the obtained resin film-forming sheet and the tantalum wafer is improved, and the adhesion is improved. The tendency of the value of force (α 1). Therefore, the content of the structural unit derived from the epoxy group-containing monomer in the acrylic polymer (A1) is preferably as small as possible.

The content of the structural unit (a3-2) derived from the epoxy group-containing monomer in the acrylic polymer (A1) used as one aspect of the present invention is from the above viewpoint with respect to the acrylic polymer ( The total structural unit (100% by mass) of A1) is preferably from 0 to 15% by mass, preferably from 0 to 10% by mass, more preferably from 0 to 5% by mass, most preferably from 0 to 3.5% by mass.

Examples of the epoxy group-containing monomer include glycidyl (meth) acrylate, β -methyl glycidyl (meth) acrylate, and (3,4-epoxycyclohexyl)methyl (A). Ethylene group such as acrylate or 3-epoxycyclo-2-hydroxypropyl (meth) acrylate containing (meth) acrylate; glycidyl crotonate, allyl glycidyl ether The like includes a non-propylene epoxy group or the like.

When an epoxy-based thermosetting component is used as the curable component (B) to be described later, the carboxyl group reacts with the epoxy group in the epoxy-based thermosetting component, so that the acrylic polymer (A1) is derived from The less the content of the structural unit containing a carboxyl group-containing monomer, the better.

When an epoxy-based thermosetting component is used as the curable component (B), the content of the structural unit (a3-3) derived from the carboxyl group-containing monomer used in one aspect of the present invention is relative to the acrylic polymer ( The total structural unit (100% by mass) of A1) is preferably 0 to 10% by mass, preferably 0 to 5% by mass, more preferably 0 to 2% by mass, most preferably 0% by mass (without structural unit ( A3-3)).

In addition, in the present specification, the acrylic polymer having a mass average molecular weight of 20,000 or more derived from a structural unit containing an epoxy group-containing monomer has thermosetting property, but is not a curable component (B), and is contained in a polymer. The concept of ingredient (A).

Examples of the carboxyl group-containing monomer include (meth)acrylic acid, maleic acid, fumaric acid, itaconic acid, and the like.

The content of the structural unit (a3) in the acrylic polymer (A1) used in one aspect of the present invention is preferably 0 to 30 by mass based on the total structural unit (100% by mass) of the acrylic polymer (A1). % is preferably from 1 to 20% by mass, more preferably from 2 to 10% by mass.

(non-acrylic resin (A2))

The sheet for forming a resin film according to an aspect of the present invention may optionally contain a non-acrylic polymer (A2) as a polymer component other than the acrylic polymer (A1).

Examples of the non-acrylic polymer (A2) include polyester, phenoxy resin, polycarbonate, polyether, polyurethane, polyoxyalkylene, and rubber-based polymer.

These non-acrylic polymers (A2) can be used individually or in combination of 2 or more types.

The mass average molecular weight (Mw) of the non-acrylic polymer (A2) is preferably 20,000 or more, preferably 20,000 to 100,000, more preferably 20,000 to 80,000.

[hardening component (B)]

The curable component (B) cures the sheet for forming a resin film, and shares the task of forming a hard resin film, and has a mass average molecular weight (Mw) of less than 20,000.

The sheet for forming a resin film used in the present invention is preferably a curable component (B), and at least one of a thermosetting component (B1) and an energy ray curable component (B2) is preferable, and the sheet for forming a resin film is suppressed. From the viewpoint of the coloration of the formed resin film, the thermosetting component is contained from the viewpoint of sufficiently proceeding the curing reaction and reducing the cost. (B1) is better.

The thermosetting component (B1) is preferably a compound having a functional group which is at least reacted by heating, and more preferably contains a compound (B11) having an epoxy group.

Further, the energy ray curable component (B2) is preferably a compound (B21) having a functional group which is reacted by irradiation with energy rays.

The functional groups having the hardenable components react with each other and harden by forming a three-dimensional network structure.

By using the component (A) in combination, the mass average molecular weight (Mw) of the curable component (B) is such that the viscosity of the composition of the material for forming the sheet for forming a resin film is suppressed, and the workability is improved. In terms of opinion, the amount is less than 20,000, preferably 10,000 or less, more preferably 100 to 10,000.

(thermosetting component (B1))

As the thermosetting component (B1), an epoxy thermosetting component is preferable.

The epoxy-based thermosetting component is preferably a compound (B11) having an epoxy group and a thermosetting agent (B12).

Examples of the epoxy group-containing compound (B11) (hereinafter also referred to as "epoxy compound (B11)") include polyfunctional epoxy resins, bisphenol A, diglycidyl ether, and hydrogenated products thereof. Novolac type epoxy resin such as cresol novolac epoxy resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F An epoxy compound having two or more functional groups in the molecule such as an epoxy resin or a phenylene skeleton epoxy resin.

These epoxy compounds (B11) can be used individually or in combination of 2 or more types.

In the above, from the viewpoint of adjusting the adhesion (α 1) and ( β 1) of the sheet for forming a resin film to the above range, it is selected from the group consisting of a novolac type epoxy resin and a biphenyl type epoxy resin. In view of adjusting the adhesion (α 1) of the sheet for forming a resin film to the above range, it is preferable to contain a biphenyl type epoxy resin, and a biphenyl aralkyl type ring is preferable. Oxygen resin is better.

The total content of one or more selected from the group consisting of a novolac type epoxy resin and a biphenyl type epoxy resin is preferably 70 to 100% by mass based on the total amount (100% by mass) of the epoxy compound (B11). It is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, most preferably 95 to 100% by mass.

In addition, the content of the biphenyl type epoxy resin is based on the total amount (100% by mass) of the epoxy compound (B11) from the viewpoint of adjusting the adhesion force (α 1) of the sheet for forming a resin film to the above range. ), preferably 70 to 100% by mass, preferably 80 to 100% by mass, more preferably 90 to 100% by mass, most preferably 95 to 100% by mass.

The content of the epoxy compound (B11) is preferably from 1 to 500 parts by mass, preferably from 3 to 300 parts by mass, more preferably from 5 to 150 parts by mass, most preferably from 10 parts by mass to 100 parts by mass of the component (A). 100 parts by mass.

(thermal hardener (B12))

The heat hardener (B12) functions as a hardener for the epoxy compound (B11).

A compound having two or more functional groups reactive with an epoxy group in one molecule of the thermosetting agent is preferred.

Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amine group, a carboxyl group, and an acid anhydride. Among these, a phenolic hydroxyl group, an amine group, or an acid anhydride is preferred, a phenolic hydroxyl group and an amine group are preferred, and an amine group is more preferred.

Examples of the phenol-based thermosetting agent having a phenol group include a polyfunctional phenol resin, a biphenol, a novolac type phenol resin, a dicyclopentadiene type phenol resin, a neophenol type phenol resin, and an aralkyl type phenol resin.

Examples of the amine-based thermosetting agent having an amine group include dicyanoguanamine (DICY) and the like.

These thermosetting agents (B12) can be used individually or in combination of 2 or more types.

From the viewpoint of adjusting the adhesion (α 1) and ( β 1) of the sheet for forming a resin film to the above range, it is preferable to contain a phenol-based thermosetting agent.

The content of the phenolic thermosetting agent is preferably from 50 to 100% by mass, preferably from 70 to 100% by mass, more preferably from 80 to 100% by mass, based on the total amount (100% by mass) of the thermosetting agent (B12). The best is 90 to 100% by mass.

The content of the heat hardener (B12) is relative to the epoxy compound (B11) 100 parts by mass, preferably 0.1 to 500 parts by mass, preferably 1 to 200 parts by mass.

Further, in the sheet for forming a resin film according to an aspect of the invention, the adhesion (α 1) and ( β 1) of the sheet for forming a resin film are adjusted to the above range, and the epoxy compound (B1) is used. The biphenyl type epoxy resin is contained, and the phenol type thermosetting agent is contained as a thermosetting agent (B12), and it is preferable to use two components.

In addition, it is more preferable that the polymer component (A) contains the acrylic polymer (A1) having the structural unit (a2-1) derived from the nitrile monomer.

(hardening accelerator (B13))

The sheet for forming a resin film according to an aspect of the present invention may further contain a curing accelerator (B13) from the viewpoint of adjusting the curing rate by heating of the sheet.

The hardening accelerator (B13) is preferably a thermosetting component (B1), and an epoxy compound (B11) is preferably used.

Examples of the curing accelerator (B13) include tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylethanolamine, and tris(dimethylmethylamine)phenol; 2-methylimidazole , 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dimethylolimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, etc. Imidazoles; organic phosphines such as tributylphosphine, diphenylphosphine, and triphenylphosphine; tetraphenylboron salts such as tetraphenylphosphonium tetraphenylborate and triphenylphosphine tetraphenylborate.

These hardening accelerators (B13) may be used alone or in combination of two or more. use.

The content of the hardening accelerator (B13) is 100 masses from the total of the epoxy compound (B11) and the heat hardener (B12) from the viewpoint of improving the adhesion of the resin film formed of the sheet for forming a resin film. The amount is preferably 0.01 to 10 parts by mass, preferably 0.1 to 6 parts by mass, more preferably 0.3 to 4 parts by mass.

(energy ray hardening component (B2))

As the energy ray curable component (B2), although the compound (B21) having a functional group which is reacted by irradiation with energy rays can be used alone, the photopolymerization initiator (B22) which is combined with the compound (B21) is used. good.

(Compound (B21) having a functional group reactive by irradiation with energy rays)

The compound (B21) having a functional group reactive by energy ray irradiation (hereinafter also referred to as "energy ray-reactive compound (B21)") may, for example, be trimethylolpropane triacrylate or pentaerythritol triacrylate. Ester, pentaerythritol tetraacrylate, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol hexaacrylate, 1,4-butanediol ester diacrylate, 1,6-hexanediol diacrylate, oligoester acrylate, Polyurethane acrylate oligomer, epoxy acrylate, polyether acrylate, itaconic acid oligomer, and the like.

The energy ray reactive compounds (B21) may be used singly or in combination 2 More than one kind.

Further, the energy ray-reactive compound (B21) preferably has a mass average molecular weight (Mw) of from 100 to 30,000, preferably from 300 to 10,000.

The content of the energy ray-reactive compound (B21) is preferably from 1 to 1,500 parts by mass, preferably from 3 to 1200 parts by mass, per 100 parts by mass of the component (A).

(Photopolymerization initiator (B22))

By the photopolymerization initiator (B22) used in combination with the energy ray-reactive compound (B21), the polymerization hardening time is shortened, and the sheet for forming a resin film can be cured even if the amount of light irradiation is reduced.

The photopolymerization initiator (B22) may, for example, be a benzoin compound, an acetophenone compound, a mercaptophosphine oxide compound, a titanocene compound, a thioxanthone compound or a peroxide compound.

More specific examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyl diphenyl group. Sulfide, tetramethylthiuram, azobisisobutyronitrile, dibenzyl, butanedione, β -crawling quinone, 2,4,6-trimethylbenzimidium diphenylphosphine oxide, and the like.

These photopolymerization initiators may be used alone or in combination of two or more.

The content of the photopolymerization initiator (B22) is sufficient for the curing reaction of the sheet for forming a resin film, and is preferably 100 parts by mass based on 100 parts by mass of the energy ray-reactive compound (B21) from the viewpoint of suppressing the generation of the residue. It is 0.1 to 10 parts by mass, preferably 1 to 5 parts by mass.

The content of the curable component (B) in the sheet for forming a resin film of the aspect of the invention is preferably from 5 to 50% by mass, preferably from 5 to 50% by mass, based on the total amount of the sheet for forming a resin film (100% by mass). 8 to 40% by mass, more preferably 10 to 30% by mass, most preferably 12 to 25% by mass.

Further, the "content of the curable component (B)" means the epoxy compound (B11), the thermosetting agent (B12), the thermosetting component (B1) containing the curing accelerator (B13), and the energy ray. The total content of the reactive compound (B21) and the energy ray-curable component (B2) containing the photopolymerization initiator (B22).

The total content of the polymer component (A) and the curable component (B) in the sheet for forming a resin film, which is one aspect of the present invention, is preferably the total amount (100% by mass) of the sheet for forming a resin film. 40% by mass or more, preferably 50% by mass or more, more preferably 60% by mass or more, and most preferably 70% by mass or more.

[Inorganic filler (C)]

The sheet for forming a resin film according to an aspect of the present invention may further contain an inorganic filler (C).

By containing the inorganic filler (C), the thermal expansion parameter of the resin film formed by the sheet for forming a resin film can be adjusted to a proper range, and the thermal expansion parameter of the wafer with the resin film can be optimized, and the embedded semiconductor wafer can be improved. The reliability of semiconductor devices. Further, the moisture absorption rate of the resin film formed of the sheet for forming a resin film can also be lowered.

As the inorganic filler (C), for example, vermiculite, oxidation Powders such as aluminum, talc, calcium carbonate, titanium oxide, iron oxide, tantalum carbide, boron nitride, or the like, such as spherical beads, single crystal fibers, and glass fibers.

These inorganic fillers (C) may be used alone or in combination of two or more.

These medium vermiculite and alumina are preferred.

The average particle diameter of the inorganic filler (C) is preferably 400 nm or less, and preferably 300 nm or less from the viewpoint of adjusting the surface roughness (Ra) of the surface (α) of the sheet for forming a resin film to the above range. More preferably, it is 200 nm or less, and is preferably 100 nm or less. On the other hand, from the viewpoint of setting the reliability of the wafer with the resin film produced using the sheet for forming a resin film, the reliability is preferably 10 nm or more, preferably 20nm or more.

Further, the average particle diameter of the inorganic filler (C) in the present specification is a value measured by a laser diffraction scattering type particle size distribution measuring apparatus, and means a volume median diameter (D ₅₀ ).

The content of the inorganic filler (C) in the sheet for forming a resin film according to the aspect of the invention is from the viewpoint of adjusting the surface roughness (Ra) of the surface (α) of the sheet for forming a resin film to the above range. The total amount (100% by mass) of the sheet for forming a resin film is preferably from 0 to 50% by mass, preferably from 0 to 45% by mass, more preferably from 0 to 40% by mass, most preferably from 0 to 30% by mass. .

In addition, when the sheet for forming a resin film of one aspect of the present invention is a laminate having two or more layers formed of two or more kinds of compositions, it is included on the surface (α) side of the sheet for forming a resin film. Layer shape The inorganic filler (C) in the composition of the material is reduced in average particle size and also reduced in content, and the surface roughness (Ra) of the surface (α) is preferably adjusted.

On the other hand, in the composition of the material forming the layer on the surface ( β ) side, the surface roughness (Ra) of the surface (α) is not affected, and the inorganic powder having an average particle diameter of 0.01 μm or more may be blended. Filler (C').

The average particle diameter of the inorganic filler (C') is usually 0.01 to 5 μm, preferably 0.02 to 3 μm.

[Colorant (D)]

The sheet for forming a resin film according to an aspect of the present invention may further contain a coloring agent (D).

When a semiconductor film having a resin film formed of a sheet for forming a resin film is incorporated into a device, the semiconductor film having the resin film formed of the resin film-forming sheet is incorporated into the device, and the infrared rays generated by the surrounding device are shielded, thereby preventing the semiconductor wafer from being formed. Wrong action.

As the colorant (D), organic or inorganic pigments and dyes can be used.

As the dye, for example, a dye such as an acid dye, a reactive dye, a direct dye, a disperse dye, a cationic dye or the like can be used.

Further, the pigment is not particularly limited, and can be suitably selected from conventional pigments and used.

A black pigment is preferable from the viewpoint that the shielding property of electromagnetic waves or infrared rays is good and the visibility of the laser marking method is improved.

As the black pigment, for example, carbon black, iron oxide, and dioxygen are mentioned. Manganese, nicotinamide, activated carbon, etc., but carbon black is preferred from the viewpoint of improving the reliability of the semiconductor wafer.

Further, these coloring agents (D) may be used alone or in combination of two or more.

The average particle diameter of the coloring agent (D) is preferably 400 nm or less, and preferably 300 nm or less from the viewpoint of adjusting the surface roughness (Ra) of the surface (α) of the sheet for forming a resin film to the above range. More preferably, it is 200 nm or less, and it is preferably 100 nm or less, and preferably 10 nm or more, preferably 20 nm or more.

Further, the average particle diameter of the colorant (D) in the present specification is a value measured by a laser diffraction scattering type particle size distribution measuring apparatus, and means a volume median diameter (D ₅₀ ).

The content of the coloring agent (D) in the sheet for forming a resin film of the aspect of the invention is preferably 0.01 to 30% by mass, preferably 0.05, based on the total amount (100% by mass) of the sheet for forming a resin film. ~25% by mass, more preferably 0.1 to 15% by mass, most preferably 0.15 to 5% by mass.

[Coupling agent (E)]

The sheet for forming a resin film according to an aspect of the present invention may further contain a coupling agent (E).

By containing the coupling agent (E), the heat resistance of the obtained resin film formed of the sheet for forming a resin film can be prevented, and the water resistance can be improved. In addition, the adhesion of the end portion after attachment to the silicon wafer is also improved.

As coupling agent (E), with component (A) or component The compound of the functional group of (B) is preferably a compound, and the decane coupling agent is more preferable.

Examples of the decane coupling agent include γ-glycidylpropyltrimethoxy decane, γ-glycidylmethyldiethoxy decane, and β- (3,4-epoxycyclohexyl)ethyltrimethoxy decane. , γ-(methacryl oxime) trimethoxy decane, γ-aminopropyl trimethoxy decane, N-6-(aminoethyl)-γ-aminopropyltrimethoxy decane, N-6-(aminoethyl) - γ-aminopropyl methyldiethoxy decane, N-phenyl-γ-aminopropyltrimethoxy decane, γ-ureidopropyltriethoxy decane, γ-mercaptopropyltrimethoxy decane, γ - propyl propyl dimethoxy decane, bis (3-triethoxymethyl decyl propyl) tetrasulfane, methyl trimethoxy decane, methyl triethoxy decane, ethylene trimethoxy decane, ethylene triethyl Alkoxy decane, imidazolium, and the like.

These coupling agents (E) may be used alone or in combination of two or more.

As the coupling agent (E), an oligomer type coupling agent is preferred.

The molecular weight of the coupling agent (E) which also contains the oligomer type coupling agent is preferably from 100 to 15,000, preferably from 150 to 10,000, more preferably from 200 to 5,000, still more preferably from 250 to 3,000, most preferably from 350. ~2000.

Further, it is conceivable that the surface of the inorganic filler (C) is bonded to the surface of the inorganic or inorganic resin (C) by the inclusion of the coupling agent (E), and the adhesion or the adhesion is improved. The agglutinability also enhances the adhesion (α 1) of the sheet for forming a resin film.

Therefore, from the viewpoint of obtaining a sheet for forming a resin film having excellent reworkability, the content of the coupling agent (E) in the sheet for forming a resin film of one aspect of the present invention is preferably as small as possible.

The content of the coupling agent (E) in the sheet for forming a resin film of the embodiment of the present invention is preferably 3.0% by mass or less based on the total amount (100% by mass) of the sheet for forming a resin film. It is preferably 1.5% by mass or less, more preferably 0.8% by mass or less, and most preferably 0.3% by mass or less. On the other hand, the end of the resin film-forming sheet and the tantalum wafer are well set. From the viewpoint of the adhesion, and the adhesion ( β 1) of the surface ( β ) of the sheet for forming a resin film to the above range, it is preferably 0.01% by mass or more, and more preferably 0.05% by mass. More than %, more preferably 0.10% by mass or more.

[Leveling agent (F)]

Further, the sheet for forming a resin film according to an aspect of the present invention may further contain a leveling agent (F).

The adhesion (α 1) of the surface (α) of the obtained sheet for forming a resin film can be easily adjusted to the above range by containing a leveling agent (F).

Examples of the leveling agent (F) include a polyfluorene-based leveling agent, a fluorine-based leveling agent, a propylene-based leveling agent, an ethylene-based leveling agent, and a fluorine-based and propylene-based leveling agent. Wait.

These leveling agents (F) may be used alone or in combination of two or more.

From the viewpoint that the adhesion (α 1) of the surface (α) of the sheet for forming a resin film can be easily adjusted to the above range, a polyfluorene-based leveling agent is preferable.

Further, when the leveling agent (F) is contained in the sheet for forming a resin film, the adhesion (α 1) of the surface (α) is easily adjusted to the above range, and the adhesion ( β 1 ) of the surface ( β ) is lowered, which is lowered. The reworkability of the sheet for forming a resin film. Therefore, on the surface ( β ) side of the sheet for forming a resin film, the content of the leveling agent is preferably as small as possible.

From the viewpoint of adjusting the adhesion (α 1) of the surface (α) of the obtained sheet for forming a resin film to the above range, the content of the leveling agent (F) is based on the total amount of the sheet for forming a resin film. (100% by mass) is preferably 0.010% by mass or more, preferably 0.050% by mass or more, and more preferably 0.100% by mass or more.

In addition, the content of the leveling agent (F) is based on the total amount of the sheet for forming a resin film from the viewpoint of adjusting the adhesion ( β 1) of the surface ( β ) of the sheet for forming a resin film to the above range. (100% by mass) is preferably 0.500% by mass or less, preferably 0.300% by mass or more, and more preferably 0.200% by mass or more.

In the case where the sheet for forming a resin film of the present invention contains a sheet of a leveling agent, the resin is used as the resin, and the pressure-sensitive adhesive sheet (α 1) and ( β 1) of the sheet for forming a resin film are adjusted in a well-balanced manner. The film forming sheet is preferably a layered sheet having a layer formed of a composition (α') containing a leveling agent and a layer formed of a layer substantially composed of a composition ( β ') containing no leveling agent. .

The composition (α') is a material for forming a layer on the surface (α) side of the sheet for forming a resin film, and the composition ( β ') is a material for forming a layer on the surface ( β ) side of the sheet for forming a resin film.

The content of the leveling agent (F) in the composition (α') is an active ingredient contained in the composition (α') from the viewpoint of adjusting the adhesion (α 1) of the surface (α) to the above range. Total amount (100 mass) %), preferably from 0.010 to 10% by mass, preferably from 0.050 to 7% by mass, more preferably from 0.100 to 5% by mass, most preferably from 0.150 to 2% by mass.

On the other hand, the content of the leveling agent (F) in the composition ( β ') is from the viewpoint of adjusting the adhesion ( β 1 ) of the surface ( β ) to the above range, with respect to the composition ( β ' The total amount (100% by mass) of the active ingredient contained is preferably from 0 to 0.500% by mass, preferably from 0 to 0.100% by mass, more preferably from 0 to 0.010% by mass, most preferably from 0 to 0.001% by mass.

[General purpose additive (G)]

In the sheet for forming a resin film to be used in one aspect of the present invention, a general-purpose additive (G) may be contained in addition to the above-mentioned components as long as the effects of the present invention are not impaired.

Examples of the general-purpose additive (G) include a crosslinking agent, a plasticizer, an antistatic agent, an antioxidant, an ion trapping agent, a deaerator, a chain transfer agent, and the like.

It is preferred to include a crosslinking agent in these.

Examples of the crosslinking agent include an isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent, a metal chelate crosslinking agent, an amine crosslinking agent, and an amine resin crosslinking agent. Wait. These crosslinking agents can be used individually or in combination of 2 or more types.

The content of the general-purpose additives (G) in the sheet for forming a resin film according to an aspect of the invention is preferably from 0 to 10% by mass based on the total amount (100% by mass) of the sheet for forming a resin film. Good for 0 to 5 mass%, more preferably 0 to 2 mass%.

<Method for Producing Sheet for Forming Resin Film>

The method for producing the sheet for forming a resin film which is one aspect of the present invention is not particularly limited, and it can be produced by a conventional method.

For example, a resin film-forming composition containing the above-described respective components of the material for forming a sheet for forming a resin film is prepared, and then an organic solvent is appropriately added and diluted to obtain a solution for forming a resin film. Then, a coating film is formed by applying a solution of the resin film-forming composition onto a support sheet by a conventional coating method, and the coating film is dried to produce a sheet for forming a resin film.

In addition, when the sheet for forming a resin film of the embodiment of the present invention is a coating of two or more layers, the method for producing the sheet for forming a resin film may be, for example, coating a resin on two or more supporting sheets. A method of forming a coating film by a solution of a film forming composition, and bonding the coating film to form a film of the coating film, followed by drying and manufacturing.

The organic solvent used for the preparation of the solution for forming the resin film may, for example, be toluene, ethyl acetate or methyl ethyl ketone.

The solid content concentration of the solution of the resin film-forming composition in the case where the organic solvent is blended is preferably from 10 to 80% by mass, preferably from 20 to 70% by mass, more preferably from 30 to 65% by mass.

Examples of the coating method include a spin coating method, a spray coating method, a bar coating method, a knife coating method, a roll coating method, a roll coating method, a knife coating method, and a mold. Coating method, gravure coating method, and the like.

The thickness of the sheet for forming a resin film according to an aspect of the present invention can be appropriately set depending on the application, and is preferably from 3 to 300 μm, preferably from 5 to 250 μm, more preferably from 7 to 200 μm.

Further, when the sheet for forming a resin film is a multi-layered sheet composed of two or more layers, the total thickness of the multi-layered sheet is also preferably in the above range.

<Use of Sheet for Forming Resin Film>

The sheet for forming a resin film according to an aspect of the present invention is attached to the back surface of a workpiece such as a flip chip type semiconductor wafer or a semiconductor wafer or the like, and a resin film can be formed on the workpiece. This resin film has a function as a protective film for protecting the back surface of a workpiece such as a semiconductor wafer or a semiconductor wafer. For example, when attached to a semiconductor wafer, since the resin film has a function of reinforcing the wafer, damage of the wafer or the like can be prevented.

In other words, the sheet for forming a resin film according to an aspect of the present invention is preferably a sheet for forming a protective film for forming a protective film on a tantalum wafer.

Further, the resin film formed of the sheet for forming a resin film according to one aspect of the present invention can also impart a function as a film. In other words, when the resin film formed by using the sheet for forming a resin film of one aspect of the present invention has a function as a film, the wafer having the resin film can be bonded to other substrates such as a pad portion or another semiconductor wafer. On the material (on the wafer loading portion), productivity can be improved in order to manufacture a semiconductor device.

In other words, the sheet for forming a resin film which is one of the aspects of the present invention for forming a film on the wafer may be a film for forming a film.

[Configuration of Composite Sheet for Resin Film Formation]

The composite sheet for forming a resin film of the present invention (hereinafter, simply referred to as "composite sheet") has a structure in which a sheet for forming a resin film of the present invention which can form the above-mentioned resin film is laminated on a support sheet.

Further, the form of the composite sheet according to one aspect of the present invention is not particularly limited, and for example, it may be in the form of a long adhesive tape or a leaf label.

Fig. 1 is a cross-sectional view showing a composite sheet for forming a resin film according to an aspect of the present invention.

As a composite sheet of one aspect of the present invention, as shown in Fig. 1 (a), a composite sheet 1a having a structure in which a sheet 10 for forming a resin film is directly laminated on a support sheet 11 is exemplified.

The shape of the sheet 10 for forming a resin film as a composite sheet according to an aspect of the present invention may have a shape which is substantially the same as the shape of the wafer to be placed or a shape of the shape of the wafer.

Further, the composite sheet 1a of the first embodiment of Fig. 1(a) has a shape similar to that of the resin film forming sheet 10, but the shape of the resin film forming sheet 10 may be compared as shown in Fig. 1(b). The composite sheet 1b of which the shape of the sheet 11 is smaller is smaller.

Further, as a composite sheet according to an aspect of the present invention, as shown in Fig. 1(c), a composite sheet 1c having a ring-shaped jig-attach layer 12 can be cited.

The annular jig-attach layer 12 is provided with a jig such as a ring frame, and is provided for the purpose of improving the adhesion of the jig, and may have a substrate. (Core material) is formed by adhering a sheet or an adhesive on both sides.

Further, in the composite sheet 1c shown in Fig. 1(c), the composite sheet 1a shown in Fig. 1(a) is a composite sheet which is further provided with the jig-attach layer 12, but is a composite sheet of one aspect of the present invention. A composite sheet in which the jig-attached layer 12 is provided on the surface of the support sheet 11 of the composite sheet 1b of Fig. 1(b) may be used.

As shown in Fig. 1 (d), the composite sheet of the resin film forming sheet 10 may have a composite sheet 1d which is sandwiched between two supporting sheets 11, 11'.

In addition, similarly to the configuration of the composite sheet 1d, the support sheet 11 may be provided as another support sheet on the surface of the resin film forming sheet 10 exposed on the composite sheet 1b of Fig. 1(b).

Further, the support sheet 11 may be provided as another support sheet on the surface of the resin film-forming sheet 10 and the surface of the jig-attach layer 12 of the composite sheet 1c shown in Fig. 1(c).

<support sheet>

The composite sheet of the aspect of the invention has a supporting sheet for supporting a release sheet which prevents dust or the like from adhering to the surface of the sheet for forming a resin film, or a task of protecting a surface of the sheet for forming a resin film for a cutting step or the like. .

The support sheet used in the present invention preferably has a resin film.

As the resin film, for example, low density polyethylene (LDPE) can be cited. Polyethylene film such as film or linear low density polyethylene (LLDPE) film, ethylene ‧ propylene copolymer film, polypropylene film, polybutylene film, polybutadiene film, polymethyl pentene film, polyvinyl chloride film , vinyl chloride copolymer film, polyethylene terephthalate film, polyethylene naphthalene film, polybutylene terephthalate film, polyurethane film, ethylene ‧ vinyl acetate film, ionization Resin film, ethylene ‧ (meth) acrylate copolymer film, ethylene ‧ (meth) acrylate copolymer film, polystyrene film, polycarbonate film, polyimide film, fluororesin film, and the like.

The support sheet used as one aspect of the present invention may be a single layer film composed of one type of resin film, or a laminated film composed of two or more resin films laminated.

Further, the above resin film may be a crosslinked film.

Further, the resin film may be used as a coloring agent or a printer or the like.

Further, the resin film may be formed by extruding a thermoplastic resin, or may be stretched, or may be formed by thinning and hardening a curable resin by a specific means.

These resin films are excellent in heat resistance and have flexibility in adaptability because of their moderate flexibility. Therefore, a resin film containing a polypropylene film is preferable from the viewpoint of easily maintaining the pick-up property.

Further, the configuration of the support sheet having the resin film containing the polypropylene film may be a single layer structure composed of only a polypropylene film, or a multilayer structure composed of a polypropylene film and another resin film.

When the sheet for forming a resin film is thermosetting, the resin film constituting the supporting sheet has heat resistance, and the heat of the supporting sheet is suppressed from being damaged, whereby the disadvantage of the manufacturing process of the semiconductor device can be suppressed.

When the support sheet is used as a release sheet for preventing dust or the like from adhering to the surface of the sheet for forming a resin film, the support sheet can be easily peeled off from the sheet for forming a resin film when it is attached to the wafer or at the time of the cutting step. A resin film is preferred.

Further, as the support sheet, a resin film which has been subjected to a release treatment on the surface of the above-mentioned resin film can also be used.

As a method of the release treatment, a method of providing a release film formed of a release agent on the surface of the above-mentioned resin film is preferred.

The release agent may, for example, be a resin containing a resin selected from the group consisting of a propylene resin, an alkyd resin, a polyoxyn resin, a fluorine resin, an unsaturated polyester resin, a polyolefin resin, and a wax resin. Agents, etc.

When the support sheet is used as a dicing sheet for protecting the surface of the sheet for forming a resin film for the dicing step or the like, it is preferable that the support sheet has an adhesive sheet having an adhesive layer formed of an adhesive on the above-mentioned resin film.

When the adhesive resin to be adhered to the adhesive is a structure of an adhesive resin, for example, a propylene resin, a polyurethane resin, a rubber resin, a polyoxyalkylene resin, or a vinyl ether resin is used. In the case of the function, for example, an energy ray-curable resin or the like can be mentioned.

In one aspect of the present invention, an adhesive containing an energy ray-curable resin is preferred from the viewpoint of setting the pick-up property favorably.

Further, when an adhesive layer formed of an adhesive containing an energy ray-curable resin is provided on the resin film, the adhesive layer may be an adhesive layer which is hardened by irradiation with an energy ray, and may be hardened before the irradiation of the energy ray. Adhesive layer. Further, when a support sheet having an uncured adhesive layer before energy ray irradiation is used, the energy ray may be irradiated before the step of picking up to harden the adhesive layer.

The thickness of the support sheet is preferably from 10 to 500 μm, preferably from 20 to 350 μm, more preferably from 30 to 200 μm, although it can be suitably selected depending on the use.

Further, the thickness of the above-mentioned supporting sheet is not only the thickness of the resin film constituting the supporting sheet, but also the thickness of the adhesive layer or the release film in the case of having an adhesive layer or a release film.

<fixture layer>

The jig-attach layer may be formed of a two-sided adhesive sheet having a substrate (core material) or an adhesive composition containing an adhesive.

The base material (core material) is preferably a resin film or a polypropylene film which can be used as the above-mentioned support sheet.

In addition, examples of the pressure-sensitive adhesive include a propylene resin, a polyurethane resin, a rubber resin, a polyoxyalkylene resin, and a vinyl ether resin.

The thickness of the subsequent layer of the jig is preferably from 1 to 80 μm, preferably from 5 to 60 μm, more preferably from 10 to 40 μm.

[矽 wafer regeneration method]

In the present invention, a method of regenerating a tantalum wafer by reprocessing the resin film forming sheet by directly laminating a laminate of the surface (α) of the resin film-forming sheet of the present invention.

The method for regenerating a tantalum wafer of the present invention has the following steps (1) to (2).

Step (1): a step of attaching the adhesive layer of the adhesive sheet to the substrate and the adhesive layer on the surface ( β ) of the sheet for forming a resin film of the laminate, and the step (2): stretching step (1) A step of attaching the adhesive sheet to the surface ( β ) of the sheet for forming a resin film, and then processing the sheet for forming a resin film to be attached to the tantalum wafer.

In the method for regenerating a tantalum wafer of the present invention, when a sheet for forming a resin film of the present invention is attached to a tantalum wafer, and the case where reprocessing is required, the wafer is not damaged, and the resin film formed by the adhesion is suppressed. One of the sheets is attached to the tantalum wafer and the remaining side can be reworked, and the properties of the sheet for forming a resin film of the present invention are utilized.

Further, the method for reproducing a wafer according to an aspect of the present invention is not only applicable to a laminate on a tantalum wafer which is directly attached to the surface (α) of the sheet for forming a resin film of the present invention, and is also applicable. A laminate in a state in which the adhesion between the wafer and the resin film-forming sheet has been improved for about 24 hours.

Hereinafter, steps (1) and (2) of the method for reproducing a tantalum wafer of the present invention will be described.

<Step (1)>

The step (1) is a step of attaching the adhesive layer having the adhesive sheet of the substrate and the adhesive layer to the surface ( β ) of the resin film-forming sheet of the laminate.

The adhesive sheet used in this step has a substrate and an adhesive layer.

The resin film of the base material is preferably a resin film exemplified in the item of the above-mentioned support sheet.

The structural unit derived from butyl acrylate and acrylic acid as specified in the adhesive layer (III), and containing 100 parts by mass of a propylene-based resin having a mass average molecular weight of 600,000 to 1,000,000 and a crosslinking agent 0.01~ An adhesive layer having a thickness of 10 to 50 μm formed by 10 parts by mass of the adhesive is preferred.

However, in one aspect of the present invention, in addition to the above-mentioned adhesive, if the adhesion ( β 1 ) of the surface ( β ) can form an adhesive of the adhesive layer in the above range, it can be used.

The shape of the adhesive sheet is not particularly limited, but is the same shape as the sheet for forming a resin film or an adhesive sheet having a larger shape than the sheet for forming a resin film, from the viewpoint of the workability of the following step (2). good.

As a method of attaching the surface ( β ) of this step to the adhesive layer of the adhesive sheet, mechanical attachment or mechanical attachment may be used.

Further, when the surface (α) of the sheet for forming a resin film which the composite sheet of one aspect of the invention described above is attached to the wafer, and the surface ( β ) side has been layered to support the sheet support sheet, The cut sheet can also be used as the adhesive sheet of this step.

<Step (2)>

In the step (2), the adhesive sheet is attached to the surface ( β ) of the resin film-forming sheet in the stretching step (1), and the resin film-forming sheet attached to the tantalum wafer is further processed. The steps.

In this step, the sheet for forming a resin film of the present invention is used, and since the adhesive force (α 1) and ( β 1) of the sheet for forming a resin film are in the above range, the surface is stretched in the step (1). ( β ) is attached with an adhesive sheet, and the sheet for forming a resin film is also dragged together, and the sheet for forming a resin film can be further processed from the wafer.

The speed and angle at which the adhesive sheet is stretched are not particularly limited, and can be appropriately set.

Further, although it is also possible to use a mechanically stretched adhesive sheet in this step, it is preferable to stretch the adhesive sheet by a manual operation from the viewpoint of workability, and to reprocess the resin film forming sheet from a tantalum wafer.

Further, in the step of removing the resin film-forming sheet, the surface of the wafer may be washed with an organic solvent such as ethanol.

Through the above steps, the tantalum wafer to which the sheet for forming a resin film is attached can be regenerated.

[Examples]

The measurement methods of the mass average molecular weight (Mw) or the number average molecular weight (Mn) of each component used in Production Examples 1 to 8 are as follows.

<mass average molecular weight (Mw), number average molecular weight (Mn)>

The measurement was carried out by a gel permeation chromatography apparatus (manufactured by Tosoh Corporation, trade name "HLC-8220GPC") under the following conditions, and measured using standard polystyrene.

(measurement conditions)

Pipe column: "TSK guard column HXL-H" "TSK gel GMHXL (×2)" "TSK gel G2000HXL" (all manufactured by Tosoh Corporation)

Column temperature: 40 ° C

Developing solvent: tetrahydrofuran

Flow rate: 1.0mL/min

Manufacturing example 1~8

(Preparation of a solution of a composition for forming a resin film)

After blending the components of the type and the amount of the mixture shown in Table 1 and preparing the resin film-forming compositions (1) to (8) (hereinafter referred to as "compositions (1) to (8)"), Further, it was diluted with methyl ethyl ketone to prepare a solution of a composition having a solid concentration of 61% by mass.

Further, the blending amount of each component in Table 1 is a ratio of 100% by mass to the total amount of each component (the total blending amount of the components (A) to (G)) (unit: mass% (effective component ratio) )). In addition, the details of each component described in Table 1 are as follows.

<Polymer component (A)>

(A-1): a propylene copolymer obtained by copolymerization of methacrylate (MA) and 2-hydroxyethyl acrylate (HEA) (composition ratio: MA/HEA = 95/5 (% by mass), Mw = 80 Wan).

(A-2): a propylene copolymer obtained by copolymerization of n-butyl acrylate (BA), ethyl acrylate (EA), acrylonitrile (AN) and methyl glycidyl acrylate (GMA) (constitution ratio: BA/EA/AN/GMA=39/29/29/3 (% by mass), Mw=800,000).

(A-3): Propylene copolymerization obtained by copolymerization of n-butyl acrylate (BA), methacrylate (MA), methyl glycidyl acrylate (GMA) and 2-hydroxyethyl acrylate (HEA) (composition ratio: BA/MA/GMA/HEA=55/10/20/15 (% by mass), Mw=800,000).

(A-4): a propylene copolymer obtained by copolymerization of n-butyl acrylate (BA), ethyl acrylate (EA) and methyl glycidyl acrylate (GMA) (composition ratio: BA/EA/GMA = 53/44/3 (% by mass), Mw = 800,000).

<hardenable component (B)>

(B-1): A cresol novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name "CNA-147", which is equivalent to the epoxy compound of the above component (B11)).

(B-2): a biphenyl aralkyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name "NC-3000H", which corresponds to the epoxy compound of the above component (B11)).

(B-3): bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name "jER828", which corresponds to the epoxy compound of the above component (B11)).

(B-4): bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name "jER1055", which corresponds to the epoxy compound of the above component (B11)).

(B-5): Dicyclopentadiene type epoxy resin (manufactured by DIC Corporation, trade name "EPICLON HP-7200HH", which corresponds to the epoxy compound of the above component (B11)).

(B-6): a biphenyl aralkyl type phenol resin (manufactured by Megumi Kasei Co., Ltd., trade name "MEH-7851-H", which corresponds to the thermal curing agent of the above component (B12)).

(B-7): dicyanodiamine (manufactured by ADEKA Co., Ltd., trade name "ADEKA HARDENER 3636AS", which corresponds to the thermal curing agent of the above component (B12)).

(B-8): an imidazole-based hardening accelerator (manufactured by Shikoku Chemicals Co., Ltd., trade name "Curezol 2PHZ", which corresponds to the curing accelerator of the above component (B13)).

<Inorganic filler (C)>

(C-1): Vermiculite filler (average particle diameter = 50 nm).

(C-2): Vermiculite filler (average particle diameter = 500 nm).

<Colorant (D)>

(D-1): carbon black (average particle diameter = 28 nm).

<decane coupling agent (E)>

(E-1): decane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "KBM-403").

<Leveling agent (F)>

(F-1): Polyoxane-based leveling agent (manufactured by Momanthoff Characteristic Material Japan Co., Ltd., trade name "XF 42-334").

<General purpose additives (G)>

(G-1): Isocyanate-based crosslinking agent (manufactured by TOYOCHEM Co., Ltd., trade name "BHS 8515").

Example 1

The surface of the first support sheet (manufactured by Linda Co., Ltd., trade name "SP-PET 3811", thickness: 38 μm) composed of the resin film which has been subjected to the release treatment is applied to the release treatment surface of the production example 2 The solution of the resin film-forming composition (2) is dried to form a coating film (α').

Then, the solution of the resin film-forming composition (1) prepared in Production Example 1 was applied onto the release-treated surface of the second support sheet which was the same as the first support sheet, and dried to form a coating film ( β '). .

After that, the coating films (α') and ( β ') formed on the support sheets of the two sheets were bonded and dried at 120 ° C for 2 minutes to form a sheet of a resin film forming layer having a total thickness of two layers of 25 μm. A composite film for forming a resin film comprising the first support sheet/resin film formation sheet/second support sheet.

Further, the surface of the resin film-forming sheet exposed at the time of removal of the first support sheet in the composite sheet is "surface (α)" on the side to which the ruthenium wafer is attached, and is exposed when the second support sheet is removed. The surface of the sheet for forming a resin film is "surface ( β )".

Example 2

In the same manner as in the first embodiment, the "solution of the resin film-forming composition (2) prepared in the production example 2) was used in the same manner as in the "solution of the resin film-forming composition (3) prepared in Production Example 3). A composite sheet for forming a resin film.

Example 3

In the same manner as in the first embodiment, the "solution of the resin film-forming composition (2) prepared in the production example 2) was used in the same manner as in the "solution of the resin film-forming composition (4) prepared in Production Example 4). A composite sheet for forming a resin film.

Example 4

In the same manner as in the first embodiment, the "solution of the resin film-forming composition (2) prepared in the production example 2) was used, except that the "solution of the resin film-forming composition (5) prepared in Production Example 5 was used. A composite sheet for forming a resin film was produced.

Example 5

The release treatment surface of the first support sheet (manufactured by Linda Co., Ltd., trade name "SP-PET3811", thickness: 38 μm) composed of the resin film which has been subjected to the release treatment is coated with the preparation example 6 After forming a coating film by the solution of the resin film-forming composition (6), it was dried at 120 ° C for 2 minutes to form a sheet for forming a resin film having a thickness of 25 μm.

Then, the surface of the resin film-forming sheet formed and the peeling-treated surface of the second support sheet which is the same as the first support sheet are bonded to each other, and the first support sheet/resin film-forming sheet/second sheet is produced. A composite sheet for forming a resin film formed of a support sheet.

Comparative example 1

In the same manner as in the fifth embodiment, the "solution of the resin film-forming composition (6) prepared in the production example 6) was used, except that the "solution of the resin film-forming composition (3) prepared in Production Example 3 was used. A composite sheet for forming a resin film was produced.

Comparative example 2

In the same manner as in the fifth embodiment, the solution of the resin film-forming composition (6) prepared in the production example 6 was used, except that the solution of the resin film-forming composition (7) prepared in Production Example 7 was used. A composite sheet for forming a resin film was produced.

Comparative example 3

In the same manner as in the fifth embodiment, the solution of the resin film-forming composition (6) prepared in the production example 6 was used, except that the solution of the resin film-forming composition (8) prepared in Production Example 8 was used. A composite sheet for forming a resin film was produced.

Using the composite sheets produced in the examples and the comparative examples, the following physical property values were measured and evaluated as follows. Table 2 shows these results.

<Requirement (I): Measurement of Surface Roughness (Ra) of Surface (α) of Sheet for Forming Resin Film>

The first support sheet of the composite sheet produced in the examples and the comparative examples was removed, and a contact surface roughness meter (manufactured by Mitutoyo Co., Ltd.) was used for the surface (α) of the exposed resin film-forming sheet. In the trade name "SURFTEST SV-3000", the cutoff value λ c was set to 0.8 mm, and the evaluation length Ln was set to 4 mm, and it was measured in accordance with JIS B0601:2001.

<Requirement (II): Surface of the sheet for forming a resin film for a silicon wafer Determination of adhesion of (α) >

The first support sheet of the composite sheet produced in the examples and the comparative examples was removed, and a tape placement machine (manufactured by Linde Co., Ltd., trade name "Adwill RAD-3600 F/12") was used at 70 ° C. The surface of the exposed resin film-forming sheet (α) and the polished surface of the #2000-polished wafer (diameter: 200 mm, thickness: 600 μm) were attached while being heated.

Then, the second support sheet of the composite sheet was removed, and the exposed surface of the resin film-forming sheet ( β ) and the commercially available adhesive sheet used as the tantalum tape were attached to a hot plate heated at 70 ° C using a 2 kg roller. (The adhesive layer manufactured by Linde Co., Ltd., trade name "PET 50 (A) PAT1", width: 25 mm) was allowed to stand in an environment of 23 ° C and 50% RH (relative humidity) for 24 hours.

After standing, the tensile test was carried out under the conditions of a peeling angle of 180° and a peeling speed of 0.3 m/min using a universal testing machine (manufactured by Shimadzu Corporation, trade name "Autograph AG-IS"), and the measurement was performed by a silicon wafer. The surface is peeled off from the load of the protective film forming sheet and the enamel tape. The value of this load is set as the adhesion of the wafer to the surface (α) of the sheet for forming a resin film.

In the tensile test of the above-mentioned commercially available adhesive sheet used for the enamel tape, the interface between the protective film forming sheet and the adhesive layer of the adhesive sheet is not peeled off, and the protective film forming sheet is provided. The interface with the wafer can be stably peeled off.

<Requirement (III): Measurement of adhesion of the surface ( β ) of the sheet for forming an adhesive film of the adhesive sheet to the adhesive sheet>

A double-sided adhesive tape for fixing a sheet for forming a resin film (manufactured by Linda Co., Ltd., trade name "TL-4100S-50") was attached to a rubber roll 矽 wafer at room temperature (25 ° C). Further, the two-sided adhesive tape was selected to sufficiently fix the sheet for forming a protective film during the tensile test.

Then, the first support sheet of the double-sided adhesive tape and the first support sheet produced in the composite sheets of the examples and the comparative examples were removed, and a tape placement machine (made by Linde Co., Ltd.) under the trade name "Adwill RAD-" was used. 3600 F/12") The surface (α) of the exposed sheet for forming a resin film is attached at room temperature.

After that, the second support sheet of the composite sheet was removed, and the exposed surface of the resin film-forming sheet ( β ) and the adhesive layer of the adhesive sheet described later were attached at 23 ° C using a 2 kg roller, and 23 ° C, 50 Allow to stand for 20 minutes in an environment of %RH (relative humidity).

After standing, the tensile test was carried out under the conditions of a peeling angle of 180° and a peeling speed of 0.3 m/min using a universal testing machine (manufactured by Shimadzu Corporation, trade name "Autograph AG-IS"), and the measurement was performed by a protective film. The surface of the sheet ( β ) is used to peel off the load when the sheet is adhered. The value of this load is defined as the adhesion of the surface ( β ) of the sheet for forming a resin film to the adhesive layer of the adhesive sheet.

(Details of the adhesive sheet attached to the surface ( β ))

Used in ethylene-methyl methacrylate copolymer which has been subjected to corona treatment (composition ratio: ethylene / methyl methacrylate = 90/10 (quality) The corona-treated surface of the resin film formed of the resin film had an adhesive sheet of an adhesive layer having a thickness of 20 μm formed of the following adhesive composition.

Adhesive composition: 100 parts by mass of propylene copolymer (BA/AA=90/10 (mass ratio), Mw=700,000) obtained by copolymerization of butyl acrylate (BA) and acrylic acid (AA), blending Toluene diisocyanate-based crosslinking agent (trade name "Coronate L", manufactured by NIPPON POLYURETHANE INDUSTRY) was used in an amount of 5 parts by mass.

<Measurement of Storage Elastic Modulus at 23 ° C of Sheet for Forming Resin Film>

A test film having a thickness of 0.18 mm, a width of 4.5 mm, and a length of 20.0 mm was produced by laminating a sheet for forming a resin film which was formed by removing the support sheets of the composite sheets produced in the examples and the comparative examples.

For the test sample, a 23 ° C storage of a sheet for forming a resin film was measured in a tensile mode at a frequency of 11 Hz, 23 ° C, and an atmosphere using a dynamic viscoelasticity measuring device (trade name "DMA Q800" manufactured by TA Instruments Co., Ltd.). Modulus of elasticity (unit: GPa).

<Measurement of contact angle of water to the surface ( β ) of the sheet for forming a resin film>

The second support sheet of the composite sheet produced in the examples and the comparative examples was removed, and 10 ml of distilled water was dropped on the surface ( β ) of the exposed resin film-forming sheet, and then left to stand for 10 minutes.

After standing, an automatic contact angle measuring device (manufactured by KRUSS, trade name "DSA 100S") was used to measure the angle at which the surface ( β ) and the water droplets were formed, and the angle was set as "the contact angle with respect to the water of the surface ( β )" .

<Evaluation (1): Reworkability of Sheet for Forming Resin Film>

The first support sheet of the composite sheet produced in the examples and the comparative examples was removed, and a tape placement machine (manufactured by Linde Co., Ltd., trade name "Adwill RAD-3600 F/12") was used. The surface of the exposed resin film-forming sheet (α) and the polished surface of the #2000-polished wafer (diameter: 200 mm, thickness: 600 μm) were attached while heating, and then, at 23 ° C, 50% RH ( Allow to stand for 24 hours in an environment of relative humidity.

After standing, the second support sheet of the composite sheet was removed, and the surface ( β ) of the exposed resin film-forming sheet was attached at room temperature (25 ° C) with a commercially available general-purpose dicing tape (Lindeke) The surface of the adhesive layer of the product name "Adwill D-510T", the adhesive sheet of the adhesive layer formed of the specific adhesive (III), and the surface of the adhesive layer was allowed to stand for 20 minutes.

After that, the general-purpose dicing tape is stretched by manual operation, and when the resin film-forming sheet is reprocessed from the enamel wafer, it is observed whether it can be reworked, and whether or not the residue on the surface of the ruthenium wafer after reprocessing is attached, The reworkability of the sheet for forming a resin film was evaluated by the following criteria.

A: The sheet for forming a protective film can be completely peeled off from the wafer. No residue of the protective film forming sheet which was visually confirmed was observed on the wafer after the rework.

B: A sheet for forming a protective film can be peeled off from the wafer. Although some of the remaining sheets of the protective film forming sheet were observed on the wafer after reprocessing, if it was wiped with ethanol, it was completely removed.

C: The wafer was damaged during the regeneration, or the wafer was reprocessed without damaging the wafer. However, it was confirmed that the residue of the protective film forming sheet which is difficult to use the degree of wiping with ethanol was confirmed on the wafer after the reprocessing.

<Evaluation (2): Adhesion of the end portion of the sheet for forming a resin film>

The first support sheet of the composite sheet produced in the examples and the comparative examples was removed, and a tape placement machine (manufactured by Linde Co., Ltd., trade name "Adwill RAD-3600 F/12") was used. The surface of the exposed resin film-forming sheet (α) and the polished surface of the #2000-polished wafer (diameter: 200 mm, thickness: 600 μm) were attached while heating, and then the second support sheet was removed. A wafer and a film for forming a resin film are attached.

After that, the end portion of the tantalum wafer to which the resin film-forming sheet was attached was visually observed, and the end portion of the resin film-forming sheet was evaluated by the following criteria based on the number of curls or defects of 0.5 mm or more. .

A: The number of curls or missings of 0.5 mm or more is 0.

B: The number of curls or missings of 0.5 mm or more is 1 to 4.

C: The number of crimps or deletions of 0.5 mm or more is 5 or more.

As is apparent from Table 2, the sheet for forming a resin film produced in Examples 1 to 5 of one aspect of the present invention was excellent in both reworkability and end sealability.

On the other hand, in the sheet for forming a resin film of Comparative Example 1, since the value of the adhesion force ( β 1) of the surface ( β ) is low, when the sheet for forming a resin film is processed by using an adhesive sheet, the resin film is formed. Part of the sheet remains on the tantalum wafer as a result of deterioration in reworkability.

Further, in the sheet for forming a resin film of Comparative Example 3, since the value of the adhesion force (α 1) of the surface (α) is high, the process of reworking the adhesive sheet using the sheet for forming a resin film causes damage to the wafer. It is the result of deterioration of reworkability.

Further, in the resin film forming sheet of Comparative Example 2, although the reworkability was good, the end portion after the bonding of the tantalum wafer was a result of deterioration in adhesion.

[Industrial use possibility]

The sheet for forming a resin film according to an aspect of the present invention is suitably used as a material for forming a protective film for protecting the back surface of a semiconductor wafer, or as a material for forming a film which can be attached to a die pad portion or other portions.

Claims (10)

A sheet for forming a resin film for attaching to a tantalum wafer, and forming a sheet of a resin film on the tantalum wafer, and satisfying the following requirements (I) to (III), and the element (I): The surface roughness (Ra) of the surface (α) of the sheet for forming a resin film and the side of the bonding wafer is 50 nm or less, and the surface (α) of the surface of the resin film forming sheet (α) for the wafer Adhesive force (α 1) is 1.0 to 7.0 N/25 mm, and the surface ( β ) of the surface of the resin film-forming sheet is formed by an adhesive on the opposite side of the side of the wafer-attached side. The adhesive layer of the adhesive sheet having the adhesive layer has an adhesive force ( β 1) of 4.0 N/25 mm or more, and the adhesive contains a structural unit derived from butyl acrylate and acrylic acid, and has a mass average molecular weight of 600,000~ 100 parts by mass of one million acrylic resin and 0.01 to 10 parts by mass of the crosslinking agent, and the adhesive sheet has an adhesive layer having a thickness of 10 to 50 μm. The sheet for forming a resin film according to the first aspect of the invention, wherein the storage elastic modulus at 23 ° C is 0.10 to 20 GPa. The sheet for forming a resin film according to the first or second aspect of the invention, wherein the surface ( β ) of the sheet for forming a resin film has a contact angle with respect to water of 70 to 110°. The sheet for forming a resin film according to the first or second aspect of the invention, wherein the polymer component (A) and the curable component (B) are contained. The sheet for forming a resin film according to the fourth aspect of the invention, wherein the polymer component (A) contains an acrylic polymer (A1). The sheet for forming a resin film according to claim 5, wherein the acrylic polymer (A1) has a structural unit derived from an alkyl (meth) acrylate (a1) and a structural unit derived from a nitrile monomer. (a2) an acrylic copolymer. A sheet for forming a resin film according to claim 1 or 2, wherein the sheet for forming a protective film is formed on a crucible wafer. A composite sheet for forming a resin film, which comprises a sheet for forming a resin film according to any one of the first to seventh aspects of the invention. The composite sheet for forming a resin film according to the eighth aspect of the invention, wherein the sheet for forming a resin film has a configuration in which two sheets of support sheets are sandwiched. A method for regenerating a tantalum wafer by directly attaching a laminate of a surface (α) of a sheet for forming a resin film according to any one of claims 1 to 7 to a wafer, and processing the resin a method of regenerating a tantalum wafer by using a sheet for forming a film, and having the following steps (1) to (2), wherein the step (1) is applied to the surface (β) of the sheet for forming a resin film of the laminate; a step of attaching the adhesive layer having an adhesive sheet of a substrate and an adhesive layer, and the step (2): adhering the adhesion to the surface (β) of the resin film-forming sheet in the stretching step (1) The sheet is processed to reprocess the resin film forming sheet attached to the tantalum wafer.